EP1210304B1 - Nouvelle composition et emulsif - Google Patents

Nouvelle composition et emulsif Download PDF

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Publication number
EP1210304B1
EP1210304B1 EP00962050A EP00962050A EP1210304B1 EP 1210304 B1 EP1210304 B1 EP 1210304B1 EP 00962050 A EP00962050 A EP 00962050A EP 00962050 A EP00962050 A EP 00962050A EP 1210304 B1 EP1210304 B1 EP 1210304B1
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EP
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Prior art keywords
adduct
derivative
emulsion
compound
emulsifier
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German (de)
English (en)
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EP1210304A1 (fr
Inventor
Willem George Boer
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Chemical Services Pty Ltd
Chemical Services Ltd
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Chemical Services Pty Ltd
Chemical Services Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/60—Two oxygen atoms, e.g. succinic anhydride
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
    • C06B47/14—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase comprising a solid component and an aqueous phase
    • C06B47/145—Water in oil emulsion type explosives in which a carbonaceous fuel forms the continuous phase
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16—Amines or polyamines

Definitions

  • This invention relates to novel compounds or compositions and methods of preparing same.
  • the invention also relates to emulsifiers, especially to emulsifiers for use in explosive compositions, especially emulsion explosive compositions.
  • the invention further relates to explosive compositions especially emulsion explosive compositions.
  • Emulsion explosives are in large scale commercial use around the world. They are made up of two inmiscible liquid phases in a stable emulsion. Usually such an emulsion comprises a discontinuous aqueous phase in a continuous lipid phase.
  • the aqueous phase usually contains a high concentration of oxidiser salts such as ammonium, sodium or calcium nitrates.
  • the lipid phase acts as a fuel and usually consists of selected petroleum products (oils).
  • An emulsifier in the form of a surface-active chemical is required to form a stable, useful emulsion.
  • Emulsions are often made by mixing a hot concentrated solution of inorganic oxidiser salts in water, with a petroleum oil that has a suitable emulsifier dissolved in it.
  • the resulting emulsions are technically unusual in that they are high internal-phase invert ("water-in-oil") emulsions, are very viscous, and the highly concentrated oxidiser salts in the disperse phase droplets should not crystallise out on cooling of the emulsion as one would expect. Durable, stable supersaturation occurs in these droplets. When crystallisation does occur, the explosive capability of the emulsion diminishes and is lost. This is a good fail-safe feature for old explosives but it is most undesirable in most commercial explosive products that need to be stored or kept for some period before actual use.
  • emulsifier which is a chemical whose molecules preferentially occupy the interface between the two phases thereby forming a barrier layer and preventing coalescence of the dispersed phase droplets.
  • the emulsion is thus rendered stable.
  • PIBSA polyisobutenyl succinic anhydride
  • the inventor of the present invention has now prepared the adduct of PIBSA with urea. It was not expected that urea would react with PIBSA to form a material useful as an emulsifier in the preparation of emulsion explosives. Surprisingly it was found that this adduct showed superior performances as an emulsifier in emulsion explosives, compared to known products such as the adduct of monoethanolamine with PIBSA.
  • a sample of an emulsion explosive composition containing the adduct of PIBSA and urea displayed a longer shelf life (slower crystallisation of oxidiser salts) than control samples made at the same time with the adduct of PIBSA and monoethanolamine. As far as the inventor is aware, last mentioned adduct has up to now given the best available shelf life.
  • R 1 and R 3 are preferably hydrogen and R 2 is preferably hydrogen or nitro.
  • X is O.
  • R 3 is preferably hydrogen.
  • R 1 is preferably hydrogen and R 2 is preferably hydrogen, hydroxyl, hydrocarbyl, hydroxyhydrocarbyl, carbamyl, 1-acetyl or amino. Alternatively R 1 and R 2 both may be carbamyl.
  • the hydrocarbyl of R 1 and R 2 is alkyl, preferably an alkyl with not more than 3 carbon atoms.
  • the hydroxyhydrocarbyl of R 1 and R 2 is -ROH wherein R is an alkyl.
  • the compound of formula I comprises a compound selected from the group consisting of urea [H 2 NCONH 2 ], hydroxyurea [HONHCONH 2 ], methylurea [CH 3 NHCONH 2 ], methylolurea [HOCH 2 NHCONH 2 ], biuret [NH 2 CONHCONH 2 ], triuret [NH 2 CONHCONHCONH 2 ], and semicarbazide (or aminourea) [NH 2 CONHNH 2 ].
  • the compound of formula I comprises urea.
  • the derivative of the adduct may comprise a heterocyclic condensate formed from the adduct where the adduct has an open acid-amide structure or it may comprise a hydrated acid formed from the adduct where the adduct is a heterocyclic condensate.
  • the polyalk(en)yl succinic anhydride preferably comprises polyisobutenyl succinic anhydride (PIBSA).
  • PIBSA polyisobutenyl succinic anhydride
  • the PIBSA may have a molecular weight from about 270 to about 2500. Preferably it is from about 950 to about 1200. In one preferred embodiment it is about 1000, and one such product is known in the trade as Lubrizol ADX 101B which has a molecular weight of about 1050.
  • the adduct is an adduct of polyalk(en)yl succinic anhydride and urea.
  • the adduct is an adduct of PIBSA and urea.
  • the compound of formula I and the polyalk(en)yl succinic anhydride may be reacted in a molar ratio from 0,5:1 to 1:1; preferably 0,5:1 to 0,75:1; most preferably 0,67:1.
  • urea Most preferably it comprises the adduct of urea and PIBSA wherein they have a molar ratio of 0,67:1.
  • the polyalk(en)yl succinic anhydride and compound of formula I may be reacted with each other at a temperature above 60°C and preferably below 140°C, prefreably at a temperature from 80 to 120°C, preferably 100 to 120°C, most preferably at 120°C.
  • the reaction time will depend on the reaction temperature and may be from 1 hour (at higher temperatures) to 22 hours (at lower temperatures). Preferably the reaction is carried out at 120°C for 1 hour.
  • the adduct which forms when PIBSA reacts with urea is one or more of the following compounds: N-(carbamyl) polyisobutenylsuccinamic acid; its condensate N-(carbamyl)-3-polyisobutenyl-2,5-pyrrolidinedione;N,N'-ketobis(polyisobutenyl -succinamic acid); and its condensate N,N'-ketobis(3-polyisobutenyl-2,5-pyrrolidinedione).
  • the preferred adduct which forms is a mixture of the above compounds, and it is believed that the acids form the major portion of such a mixture. It is also believed that if the reaction is carried out a higher temperature for a longer period of time, an increasing amount of the heterocyclic condensates will form.
  • an emulsifier comprising an adduct or derivative thereof substantially as described hereinabove.
  • the emulsifier is suitable for use as an emulsifier for water and oil emulsions, preferably as an emulsifier in an emulsion explosive composition.
  • an adduct or derivative thereof substantially as described hereinabove as an emulsifier.
  • an emulsion including an emulsifier substantially as described hereinabove.
  • an emulsion comprising a discontinuous liquid phase containing an oxygen supplying component; a continuous liquid phase of an organic medium; and an adduct or derivative thereof substantially as described hereinabove.
  • the emulsion is an emulsion explosive composition.
  • the discontinuous phase may comprise an aqueous phase and preferably it comprises an oxidiser salt dissolved in water.
  • the oxidiser salt may comprise a nitrate salt and preferably it comprises ammonium nitrate.
  • the organic medium may comprise a petroleum product, preferably an oil.
  • an explosive composition comprising a mixture of a dry explosive or oxidising salt; and an emulsion explosive composition substantially as described hereinabove.
  • the compounds may be reacted with each other under heating.
  • the products are stirred while heated above 60° and preferably below 140°C, preferably at a temperature from 80 to 120°C, preferably 100 to 120°C, most preferably at 120°C.
  • the reaction time will depend on the reaction temperature and may be from 1 hour (at higher temperatures) to 22 hours (at lower temperatures).
  • the reaction is carried out at 120°C for 1 hour.
  • the polyalk(en)yl succinic anhydride is pre-heated, preferably to about 40°C.
  • the method may also include the step of forming a heterocyclic condensate of the adduct where the adduct includes an open acid-amide structure. Alternatively it may include the step of forming a hydrated acid of the adduct where the adduct includes a condensated acid.
  • the compound of formula I and the polyalk(en)yl succinic anhydride may be provided in a molar ratio from 0,5:1 to 1:1, preferably 0,5:1 to 0,75:1, most preferably 0,67:1.
  • the reaction flask was heated to 80°C with continuous stirring for 22 hours at which point examination of small samples from the flask by infra-red absorption spectrometer showed by disappearance of the characteristic absorption peak of the anhydride part of PIBSA, that the latter had reacted essentially completely.
  • the product was then allowed to cool to room temperature.
  • Example 1 The process of Example 1 was repeated but in this case the reaction flask was heated to 120°C with continuous stirring for 1 hour, at which point examination of samples again showed that the PIBSA had reacted essentially completely.
  • the reaction flask was heated to 130°C with continuous stirring for 5 hours at which point examination of small samples from the flask by infra-red absorption spectrometer showed by disappearance of the characteristic absorption peak of the anhydride part of PIBSA, that the latter had reacted essentially completely.
  • the product was then allowed to cool to room temperature.
  • a lipid phase was prepared by diluting 105,0g of the reaction product of, in turn, example 1, example 2 or example 3 with 195,0g of a commercially available high flash point petroleum solvent known as Shellsol 2325 (trade name).
  • the emulsion was allowed to cool to room temperature.
  • Each base emulsion of example 4 (in an amount of 100,0g) was mixed with 65,7g of commercially available ammonium nitrate (known as Porous Prill Ammonium Nitrate (trade name)) supplied by African Explosives Limited. In this way three samples of a typical bulk explosive formulation were formed.
  • ammonium nitrate known as Porous Prill Ammonium Nitrate (trade name)
  • the two bulk emulsion explosive compositions derived from examples 1 and 2 were stored at ambient temperature, exposed to room air and examined weekly for a period of three months. Even after three months, these compositions were judged to have crystallised to a lesser extent than control samples made with a PIBSA/monoethanol amine emulsifier.
  • the bulk emulsion explosive composition derived from example 3 was stored at ambient temperature, exposed to room air, for a period of one week, and was judged to have retained its initial appearance and quality for that period. This was sufficient to indicate that the adduct of example 3 was capable of forming a commercially useful emulsion explosive composition, as such completely formulated compositions, in bulk explosives applications, are seldom required to undergo a delay of longer than a week before being detonated.
  • emulsions were prepared as set out in example 4. However in this case the amount of adduct was selected to provide four emulsions respectively containing 1,06; 0,91; 0,76 and 0,61 percent of the adduct on a mass/mass basis.
  • Emulsion explosives were prepared as set out in example 5 but utilising the above emulsions. In each case the emulsion explosive comprised 6 parts emulsion composition to 4 parts porous prilled ammonium nitrate (parts calculated on a mass basis).
  • Emulsion explosives containing a conventional emulsifier in the form of the adduct of PIBSA and monoethanolamine were also prepared.
  • the adduct was prepared by reacting PIBSA and the monoethanolamine in a molar ratio of 1:1 and the product was uncondensed. Using this adduct, emulsions with concentrations as set out in the previous paragraph were prepared, and the emulsion explosives were prepared in the same way as set out above.
  • the emulsion explosives were considered on a weekly basis for their storage quality.
  • the rating scale for the storage quality is as follows:
  • the product of at least example 2 made a useful doped emulsion explosive with a six-week useable shelf life at only 0.31% by mass active emulsifier in the emulsion, and a stable invert type explosives emulsion could still be made at only 0,15% by mass active emulsifier in the emulsion.
  • Present commercially used emulsifiers for emulsion explosives are quite incapable of such performance since they need higher concentrations of the emulsifier.
  • adducts of at least example 2 improved the ease with which an emulsion could be formed.
  • explosive emulsifiers in which the PIBSA/monoethanolamine headgroup is of the uncondensed (amide/acid) type are known to be capable of interacting chemically with (excess) sodium nitrite in chemically gassed emulsion.
  • emulsion break-up can occur as a result, causing gross crystallisation of oxidiser salts and total emulsion quality failure sometimes within hours of manufacture.
  • Aggravating conditions for failure are: low emulsifier dosage in the emulsion, poor refinement (large droplet size) and high unreacted nitrite levels (which can sometimes occur in commercial emulsion explosives products).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Medicinal Preparation (AREA)

Claims (19)

  1. Produit d'addition d'anhydride polyalc(én)yl succinique et d'un composé de la formule :
    Figure 00270001
    où
    R1 est hydrogène, hydroxyle, hydrocarbyle, hydroxyhydrocarbyle, carbamyle, 1-acétyle, amino, ou nitro ;
    R2 est hydrogène, hydroxyle, hydrocarbyle, hydroxyhydrocarbyle, carbamyle, 1-acétyle, amino, ou nitro ;
    R3 est hydrogène ou hydrocarbyle ; et
    X est O, S ou NH ;
    ou un dérivé d'un tel produit d'addition.
  2. Produit d'addition ou son dérivé de la revendication 1 où le composé de formule I est guanidine ou nitroguanidine.
  3. Produit d'addition ou son dérivé de la revendication 1 où le composé de formule I est thiourée.
  4. Produit d'addition ou son dérivé de la revendication 1 où X dans la formule I est en O.
  5. Produit d'addition ou son dérivé la revendication 4 où le composé de formule I comprend un composé sélectionné dans le groupe consistant en urée [H2NCONH2], hydroxyurée [HONHCONH2], méthylurée [CH3NHCONH2], méthylolurée [HOCH2NHCONH2], biuret [NH2CONHCONH2], triuret [NH2CONHCONHCONH2], et semicarbazide (ou aminourée) [NH2CONHNH2].
  6. Produit d'addition ou son dérivé de la revendication 5 où le composé de formule I est de l'urée.
  7. Produit d'addition ou son dérivé de l'une quelconque des revendications précédentes où l'anhydride polyalc(én)yl succinique comprend l'anhydride polyisobutényl succinique (PIBSA).
  8. Produit d'addition ou son dérivé de la revendication 7 où PIBSA a un poids moléculaire d'environ 950 à environ 1200.
  9. Produit d'addition ou son dérivé de la revendication 1 où l'anhydride polyalc(én)yl succinique est PIBSA et le composé de formule I est de l'urée.
  10. Produit d'addition ou son dérivé de la revendication 1 où le composé de formule I et l'anhydride polyalc(én)yl succinique sont mis à réagir à un rapport molaire de 0,5:1 à 1:1.
  11. Emulsif comprenant le produit d'addition ou son dérivé tels que revendiqués dans l'une quelconque des revendications précédentes.
  12. Emulsif de la revendication 11 qui est un émulsif pour des compositions explosives émulsion eau et huile.
  13. Utilisation d'un produit d'addition ou son dérivé de l'une quelconque des revendications 1 à 10 comme émulsif.
  14. Emulsion comprenant un émulsif de l'une quelconque des revendications 11 ou 12.
  15. Emulsion comprenant une phase liquide discontinue contenant un composant fournissant de l'oxygène ; une phase liquide continue d'un milieu organique ; et un émulsif de l'une quelconque des revendications 11 ou 12.
  16. Emulsion de la revendication 15 où la phase discontinue comprend une phase aqueuse sous la forme d'un sel oxydant dissous dans l'eau.
  17. Emulsion de la revendication 15 ou 16 où le milieu organique comprend une huile.
  18. Composition explosive comprenant un mélange d'un explosif sec ou sel oxydant ; et d'une émulsion de l'une quelconque des revendications 15 à 17.
  19. Méthode de préparation d'un composé comprenant la réaction d'un anhydride polyalc(én)yl succinique avec un composé de formule I tel qu'indiqué à la revendication 1.
EP00962050A 1999-09-02 2000-08-31 Nouvelle composition et emulsif Expired - Lifetime EP1210304B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ZA995665 1999-09-02
ZA9905665 1999-09-02
PCT/ZA2000/000154 WO2001016056A1 (fr) 1999-09-02 2000-08-31 Nouvelle composition et emulsif

Publications (2)

Publication Number Publication Date
EP1210304A1 EP1210304A1 (fr) 2002-06-05
EP1210304B1 true EP1210304B1 (fr) 2003-02-19

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EP00962050A Expired - Lifetime EP1210304B1 (fr) 1999-09-02 2000-08-31 Nouvelle composition et emulsif

Country Status (9)

Country Link
US (1) US6630596B2 (fr)
EP (1) EP1210304B1 (fr)
AP (1) AP1418A (fr)
AT (1) ATE232844T1 (fr)
AU (1) AU770608B2 (fr)
CA (1) CA2383056C (fr)
DE (1) DE60001464T2 (fr)
DK (1) DK1210304T3 (fr)
WO (1) WO2001016056A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9227221B2 (en) * 2005-09-19 2016-01-05 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Hydrophilic-core microcapsules and their formation
PL406629A1 (pl) 2011-03-29 2014-07-21 Fuelina, Inc. Paliwo hybrydowe i sposób jego wytwarzania
US10308885B2 (en) 2014-12-03 2019-06-04 Drexel University Direct incorporation of natural gas into hydrocarbon liquid fuels

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2223228A (en) * 1988-09-21 1990-04-04 Ici Plc Water-in-oil emulsion explosive

Also Published As

Publication number Publication date
WO2001016056A1 (fr) 2001-03-08
AP2002002429A0 (en) 2002-03-31
US6630596B2 (en) 2003-10-07
DK1210304T3 (da) 2003-06-10
ATE232844T1 (de) 2003-03-15
AU770608B2 (en) 2004-02-26
CA2383056A1 (fr) 2001-03-08
US20020182170A1 (en) 2002-12-05
DE60001464D1 (de) 2003-03-27
AP1418A (en) 2005-05-26
DE60001464T2 (de) 2004-01-15
AU7391500A (en) 2001-03-26
CA2383056C (fr) 2006-12-19
EP1210304A1 (fr) 2002-06-05

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